EXCHANGE 


8061  ' 
'AT 


CHLORINATION  AND  THE  FORMATION  OF  CHLORO- 
AMINES  BY  MEANS  OF  NITROQEN  TRICHLORIDE 

BY 

GEORGE  HOPKINS  COLEMAN 
B.  S.  Greenville  College,  1915 
M.  S.  University  of  Illinois,  19 19 


THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY 

IN  CHEMISTRY 
IN 

THE  GRADUATE  SCHOOL 

OF  THE 

UNIVERSITY  OF  ILLINOIS 
1921 


EASTON,  PA.: 

KSCHENBACH  PRINTING  COMPANY 
1922 


CHLORINATION  AND  THE  FORMATION  OF  CHLORO- 
AMINES  BY  MEANS  OF  NITROGEN  TRICHLORIDE 

t 

BY 

GEORGE  HOPKINS  COLEMAN 
B.  S.  Greenville  College,  1915 
M.  S.  University  of  Illinois,  1919 


THESIS 

. 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 


FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY 

IN  CHEMISTRY 

IN 
THE  GRADUATE  SCHOOL 

OF  THE 

UNIVERSITY  OF  ILLINOIS 
1921 


K ASTON,  PA.: 

ESCHENBACH  PRINTING  COMPANY 
1922 


ACKNOWLEDGMENT. 

The  writer  wishes  to  express  his  appreciation  for  the  invaluable  assist- 
ance of  Professor  Noyes,  who  suggested  the  problem  and  under  whose 
direction  this  research  was  done. 


A78667 


CHLORINATION  AND  THE  FORMATION  OF  CHLORO-AMINES 
BY  MEANS  OF  NITROGEN  TRICHLORIDE. 

Introduction. 

The  investigation  was  first  undertaken  in  the  hope  that  it  might  have 
a  bearing  on  the  general  question  of  the  positive  and  negative  character 
of  atoms  in  combination. 

A  study  of  the  reaction  between  nitrogen  trichloride  and  ethyl  bromide 
was  made  with  the  thought  that  it  might  yield  triethylamine  and  free 
chlorine  and  bromine,  or  perhaps  a  chlorobromine  compound.  A  reac- 
tion of  this  kind  would,  of  course,  be  of  much  interest  in  relation  to  the 
general  problem.  Ethyl  iodide  was  first  used,  but  it  was  found  very  diffi- 
cult to  control  the  reaction.  The  work  was  therefore  carried  out  with 
ethyl  bromide. 

No  evidence  was  found  of  the  formation  of  an  amine.  The  products 
of  the  reaction  were  ammonium  chloride,  nitrogen,  chlorine,  bromine, 
and  a  small  amount  of  a  high-boiling  liquid  residue  left  upon  distillation 
of  the  ethyl  bromide.  That  the  nitrogen  trichloride  did  act  as  a  chlorin- 
ating agent  to  a  slight  extent  was  evidenced  by  an  analysis  of  the  three 
principal  fractions  of  the  high-boiling  residue.  The  results  seemed 
to  indicate  that  these  products  were  not  the  same  as  those  found  when 
Lescoeur1  studied  the  action  of  chlorine  on  ethyl  bromide. 

To  determine  whether  or  not  nitrogen  trichloride  differs  from  free  chlor- 
ine in  its  chlorinating  action,  the  investigation  was  continued.  Ethyl 
chloride  was  used  in  place  of  ethyl  bromide  in  order  to  simplify  the  iden- 
tifications of  the  products. 

With  the  thought  of  extending  the  work  to  a  different  class  of  compounds, 
the  reaction  of  nitrogen  trichloride  was  also  tried  with  toluene,  with  ben- 
zene, and  with  benzyl  chloride.  In  each  case,  a  very  unexpected  result 
was  obtained  in  thatj  along  with  other  products  of  the  reaction,  small 
amounts  of  chlorinated  amines  were  formed. 

Theoretical. 

I.  Chlorination. — The  work  with  nitrogen  trichloride  and  ethyl 
chloride  was  carried  out  as  that  with  the  ethyl  bromide  had  been,  without 
exposure  to  light  other  than  dim  artificial  light.  The  products  of  the 

1  Lescoeur,  Bull.  soc.  chim.,  29,  483  (1878). 


6 

reaction  were  similar  to  those  obtained  with  the  ethyl  bromide.  The 
most  interesting  and  significant  feature  of  the  work  with  this  compound, 
however,  was  the  fact  that,  in  addition  to  the  usual  products  of  the  ac- 
tion of  chlorine  on  ethyl  chloride,  the  high-boiling  residue  contained  a 
relatively  large  amount  of  ethylene  chloride. 

It  has  been  quite  well  established  that  ethylene  chloride  is  not  a  product  of  the 
chlorinating  action  of  free  chlorine  on  ethyl  chloride  in  the  absence  of  a  catalytic  agent. 
As  the  products  of  this  reaction,  Regnault2  found  ethylidene  chloride,  together  with 
several  higher  chlorinated  derivatives  of  ethane,  but  no  ethylene  chloride.  Damoi- 
seau,1  although  his  experiments  were  performed  at  a  higher  temperature,  found  no 
ethylene  chloride.  Geuther4  apparently  found  traces  of  ethylene  chloride  in  his  pro- 
duct, but  thought  it  was  due  to  impurities  in  the  ethyl  chloride  used.  Stadel 5  prepared 
5  kg.  of  the  reaction  product,  which  on  careful  fractionation,  gave  no  evidence  of  ethyl- 
ene chloride.  Denzel6  also  secured  the  same  result.  However,  Victor  Meyer  and 
Miiller7  did  prepare  ethylene  chloride  from  ethyl  chloride  by  heating  equivalent  amounts 
of  antimony  pentachloride  and  ethyl  chloride  at  100°  in  sealed  tubes.  They  also  pre- 
pared ethylene  bromide  from  ethyl  bromide  and  bromine,  with  iron  filings  as  a  cata- 
lytic agent. 

As  mentioned  above,  the  work  with  the  aromatic  compounds  was  un- 
dertaken with  the  thought  of  studying  the  chlorinating  action  of  nitrogen 
trichloride  on  a  different  class  of  substances.  In  the  case  of  toluene,  it 
was  found  that  the  high-boiling  residue  left  on  distillation  of  the  toluene 
consisted  of  a  mixture  of  monochloro-toluenes  and  benzyl  chloride  to- 
gether with  higher  chlorinated  products.  Hentschel8  found  benzene 
hexachloride  as  the  product  of  the  action  of  nitrogen  trichloride  on  benzene 
in  the  sunlight.  It  might  be  pointed  out  in  this  connection  that  sunlight 
decomposes  nitrogen  trichloride  rapidly.  Probably  this  product  was 
formed  by  the  action  of  free  chlorine  on  the  benzene.  Benzene  hexa- 
chloride was  also  found  to  be  the  main  chlorination  product  of  the  tri- 
chloride with  benzene  in  this  investigation.  Although  in  most  cases,  the 
reaction  was  carried  out  in  the  dark,  an  excess  of  chlorine  was  present  in 
the  solution  soon  after  its  preparation,  as  a  result  of  the  decomposition 
of  the  trichloride. 

II.  Chloro-amines. — In  all  the  reactions  studied,  a  white  precipitate 
containing  ammonium  chloride  was  formed.  In  the  case  of  toluene, 
of  benzene  and  of  benzyl  chloride,  when  this  white  precipitate  was  dissolved 
in  water  and  an  alkali  was  added,  a  mixture  of  insoluble  amines  separated 
at  once.  With  benzene  and  with  benzyl  chloride,  the  white  precipitate 

2  Regnault,  Ann.  Chem.  Pharm.,  33,  312  (1840). 
8  Damoiseau,  Compt.  rend.,  63,  60  (1876). 
4  Geuther,  Z.  Chem.,  7,  147  (1871). 

6  Stadel,  Ann.,  195,  182  (1879). 
«  Denzel,  ibid.,  195,  204  (1879). 

7  Victor  Meyer  and  Miiller,  Ber.,  24,  4249  (1891). 

8  Hentschel,  Ber.,  30,  1436  (1897). 


was  found  to  contain  the  hydrochlorides  of  the  amines  only  when  the 
solutions  had  been  exposed  to  sunlight,  or  after  ft  stood  for  a  long  time. 
But,  in  all  cases,  if  the  solutions  from  which  the  precipitate  had  been  re- 
moved were  shaken  with  cone,  hydrochloric  acid,  amines  were  found  in 
the  aqueous  solution. 

The  properties  of  this  intermediate  compound  present  in  the  original 
solutions  are  illustrated  in  the  work  with  benzene.  It  was  found  that  it 
did  not  possess  basic  properties  and  was  not  easily  hydrolyzed  or  reduced. 
When  it  was  shaken  with  cone,  hydrochloric  acid,  free  chlorine  was  lib- 
erated and  aniline  derivatives  were  formed.  This  intermediate  com- 
pound is  probably  an  N-chloro-amine,  i.  e.,  a  chloro-amine  in  which  the 
chlorine  is  combined  with  the  nitrogen.  * 

The  work  of  Bender9  is  typical  of  that  done  by  several  investigators  on  the  prep- 
aration and  rearrangement  of  N-chloro-amines  or  substituted  nitrogen  chlorides.  N- 
chloro-acetanilide  was  prepared  from  acetanilide  and  calcium  hypochlorite.  When 
heated  to  172°,  this  compound  rearranged  to  give  £-chloro-acetanilide.  In  a  study  of 
the  characteristic  rearrangements  of  the  substituted  nitrogen  halides,  Chattaway  and 
Orton10  prepared  a  series  of  compounds  in  which  the  halogen  of  a  chloro-or  bromo-amine, 
C8H8NRX,  rearranged  successively  to  compounds  with  the  halogen  in  positions  4,2 
and  6.  The  chloro-amine  CeHzXjNRX,  which  was  finally  obtained  did  not  undergo 
further  rearrangement. 

The  action  of  nitrogen  trichloride  on  aniline,  on  methyl  aniline  and  on  dimethyl 
aniline  has  been  studied  by  Hentschel.11  When  equimolecular  parts  of  aniline  and  a  so- 
lution of  nitrogen  trichloride  in  benzene  react,  trichloro-aniline  is  formed.  This  com- 
pound may  also  be  formed  by  passing  chlorine  into  a  suspension  of  aniline  hydrochloride 
in  benzene.  Methyl  aniline  similarly  gives  trichloro-methylaniline.  Dimethyl  aniline 
gives  a  product  the  structure  of  which  was  not  determined. 

Beilstein  and  Kurbatow12  have  prepared  trichloro-aniline  and  tetrachloro-aniline 
by  chlorination  of  mono  and  dichloro-aniline.  Pentachloro-aniline  has  been  prepared 
by  Langer13  by  passing  chlorine  into  an  ether  solution  of  dichloro-aniline. 

Without  introducing  the  question  of  positive  and  negative  valence,  it 
may  be  suggested  as  a  possible  explanation  of  the  mechanism  of  the  forma- 
tion of  the  amines  that  the  nitrogen  trichloride  adds  to  the  benzene  ring 
to  give  a  compound,  CeHeNC^.Cl.  This  may  be  followed  by  the  loss  of 
hydrochloric  acid  to  give  a  chloro-amine,  C6H5NC12.  A  possible  expla- 
nation of  the  transformation  produced  by  cone,  hydrochloric  acid  may 
be  the  following.  One  molecule  of  hydrochloric  acid  adds  to  the  nitrogen 
and  is  followed  by  the  loss  of  a  molecule  of  chlorine.  This  would  leave 
an  N-monochloro-amine  which  by  a  similar  process  is  changed  to  the  true 
amine. 

0  Bender,  Ber.,  19,  2272  (1886). 

10  Chattaway  and  Orton,  Ber.,  32,  3572  (1899). 

11  Hentschel,  Ber.,  30,  2643  (1897). 

12  Beilstein  and  Kurbatow,  Ann.,  196,  230  (1879). 
11  Langer,  ibid.,  217,  120  (1882). 


H 
/Cl  / /Cl  /H 

R"N\ci  +  HC1  "^  R~N \ci "^  R~N\ci  +  Cla 

Cl 


/H 
\C1 


H 
//H  /H 

~N  \CI  ~^  R~N  \H 

Cl 


One  of  us14  has  shown  that  nitrogen  trichloride  and  hydrochloric  acid 
yield  ammonium  chloride  and  chlorine  quantitatively,  even  in  the  absence 
of  water.  A  similar  explanation  of  the  mechanism  of  the  reaction  was 
given. 

The  amines  were  extracted  with  ether  after  the  addition  of  alkali  to 
the  aqueous  solutions,  and  subsequently  studied.  From  the  method  of 
formation  and  the  presence  of  an  excess  of  chlorine  in  the  solutions  a  mix- 
ture of  chlorinated  amines  was  to  be  expected.  This  proved  to  be  the 
case,  the  products  evidently  consisting  of  mixtures  of  chlorinated  anilines 
and  toluidines,  respectively.  These  products  when  first  obtained  by 
evaporation  of  the  ether  from  a  dry  ether  solution,  were  viscous  liquids. 
In  the  case  of  the  product  from  benzene,  a  crystalline  substance  was  ob- 
tained by  recrystallization  from  ether  and  ligroin.  The  toluene  product 
behaved  quite  peculiarly  in  that,  on  standing  a  few  days,  it  changed  to  a 
dark  brittle  rosin-like  solid.  The  amine  mixture  obtained  from  benzene 
did  not  do  this.  If  chlorine  had  substituted  in  the  side  chain  of  the 
toluene  molecule,  such  a  change  could  be  explained  by  a  reaction  between 
the  chlorine  of  one  molecule  and  the  amino  group  of  another.  With  this 
in  mind,  the  action  of  nitrogen  trichloride  on  benzyl  chloride  was  tried. 
The  viscous  liquid  mixture  of  amines  obtained  from  this  reaction  solidi- 
fied in  a  few  days  as  that  from  toluene  had  done.  The  explanation  given 
then  seems  probable. 

Experimental. 

I.  Nitrogen  Trichloride  and  Ethyl  Chloride.  —  Various  methods  for  the  preparation 
of  nitrogen  trichloride  were  tried.  The  method  which  was  most  satisfactory  and  the 
one  finally  used  was  the  following.  A  solution  of  ammonium  sulfate  or  ammonium 
nitrate,  together  with  a  suitable  solvent  for  the  nitrogen  trichloride  (in  this  case  ethyl 
chloride  itself  was  used),  was  surrounded  with  a  freezing  mixture  at  —10°  to  —20°, 
and  the  chlorine  was  passed  into  this  solution  at  the  rate  of  0.2  to  0.4  g.  per  minute.  The 
solutions  were  kept  in  intimate  contact  by  means  of  a  stirrer  operated  by  a  small  mo- 
tor. When  the  reaction  was  complete,  the  ethyl  chloride  solution  was  separated  from 
the  aqueous  layer  and  dried  with  calcium  chloride.  Samples  were  taken  and  the  re- 
mainder of  the  solution  was  sealed  in  thick  -walled  glass  tubes  and  left  in  the  dark  for 
from  10  to  20  days. 

14  Noyes,  J.  Am.  Chem.  Soc.,  42,  2173  (1920). 


In  the  analysis  of  the  solutions,  the  nitrogen  was  determined  with  cone,  hydro- 
chloric acid,  according  to  the  reaction  NC1S  +  4  HC1  =  .NH4C1  +  3  C12,  a  method 
developed  by  one  of  us15  and  found  to  give  better  results  than  the  usual  sodium  sulfite 
reduction.  The  ammonia  was  then  determined  by  distillation  from  an  alkaline  solu- 
tion. The  chlorine  was  determined  in  another  sample  by  Volhard's  method,  after  it 
was  reduced  with  sodium  sulfite  and  treated  with  just  enough  potassium  permanganate 
to  oxi  dize  the  excess  of  sulfite. 

In  all,  1 105  g.  of  solution  containing  504.4  mg.  atoms  of  nitrogen  was  prepared  and 
used.  From  this  amount  the  high-boiling  residue  formed  in  the  reaction,  on  careful 
fractionation,  gave  the  following  fractions. 

TABLE  I. 
FRACTIONATION  OF  HIGH-BOILING  RESIDUE. 

Temp.  Vol.  Temp.  Vol. 

0  C.  Cc.  °  C.  Cc. 

50-58  0.25  81-84  1.00 

58-62  0.50  84-150  0.20 

62-72  0.40  150-175  0.50 

72-76  0.20  175-190  2.00 

76-81  0.25  Residue  above  190°,  0.70 

Several  of  the  usual  methods  for  distinguishing  between  ethylene  chloride  and  ethyl- 
idene  chloride  were  tried  with  the  known  substances,  but  with  the  very  small  amounts 
with  which  it  was  necessary  to  work  in  the  ca.se  of  the  fractions  obtained  above,  none  of 
these  was  found  to  be  satisfactory.  Finally  a  method  of  differentiation  was  developed 
in  which  very  small  quantities  could  be  used.  This  was  based  on  the  rates  of  hydrol- 
ysis of  the  two  chlorides  by  alkali,  followed  by  oxidation  of  the  product  of  hydrolysis 
with  alkaline  permanganate  and  the  determination  of  the  oxalate  formed  by  titration 
with  standard  permanganate  in  hot  acid  solution.  Ethylidene  chloride  was  found  to 
hydrolyze  more  rapidly  than  ethylene  chloride  and  to  give  very  much  less  oxalate  on 
oxidation.  The  titration  for  0.2  cc.  each  of  ethylene  and  ethylidene  chloride  took 
20.08  cc.  and  3.05  cc.  of  standard  permanganate  solution  respectively.  The  fractions 
of  the  chlorinated  product  corresponding  to  the  boiling  points  of  ethylene  and  ethylidene 
chloride  behaved  in  every  way  like  those  of  the  known  substances.  The  81-84°  frac- 
tions required  18.00  cc.  of  permanganate  solution  for  oxidation  of  the  oxalate  formed, 
the  58-62°  fraction,  3.90  cc.  only. 

II.  Nitrogen  Trichloride  with  Tofciene  and  with  Benzyl  Chloride. — The  solutions 
of  the  trichloride  in  toluene  and  the  other  aromatic  liquids  were  prepared  in  much  the 
same  way  as  those  in  ethyl  chloride  had  been.  Five  solutions  in  toluene  were  prepared 
totaling  1706  g.  of  solution  and  containing  921.7  mg.  atoms  of  nitrogen  and  2633.5  mg. 
atoms  of  chlorine.  The  ratio  of  chlorine  to  nitrogen  is  2.85.  After  preparation  the 
solutions  gradually  became  opalescent  and  in  the  course  of  5  or  6  hours,  quite  warm. 
In  12  to  15  hours  the  reaction  was  evidently  complete,  unless  the  solution  had  been  kept 
cool.  In  that  case,  3  or  4  days  were  required.  The  white  precipitate  which  formed  in 
the  toluene  solution  was  found  to  be  a  mixture  of  ammonium  chloride  and  the  hydro- 
chloride  of  the  amines.  From  a  solution  containing  114  mg.  atoms  of  nitrogen,  about 
1  g.  of  free  amine  was  found  in  the  white  precipitate  and  about  an  equal  amount  was 
secured  from  the  toluene  solution  by  treatment  with  cone,  hydrochloric  acid.  Thus, 
only  a  small  percentage  of  the  total  nitrogen  present  in  the  original  solution  was  found 
in  the  amines.  Of  the  remainder,  about  3/4  was  evolved  as  free  nitrogen  and  V*  formed 
ammonium  chloride.  The  toluene  solution  from  the  5  preparations  was  found  to  con- 
tain 8  to  10  g.  of  the  monochloro-toluenes,  and  10  to  12  g.  of  benzyl  chloride,  with  a 


15  Noyes,  J.  Am.  Chem.  Soc.,  43,  2178  (1920). 


10 

large  residue  boiling  above  190°.  These  fractions  were  identified  by  boiling  point  and 
other  properties. 

In  the  study  of  the  amines  some  of  the  tests  made  were  the  following.  By  the 
sodium-fusion  method  the  substance  was  found  to  contain  nitrogen  and  chlorine. 
When  a  sample  was  diazotized  and  mixed  with  an  alkaline  solution  of  /3-naphthol, 
a  bright  reddish-yellow  precipitate  was  formed.  Carbon  dioxide  was  passed  into  a 
dry  ether  solution,  but  no  amine  carbonate  was  precipitated,  proving  the  absence  of 
benzyl  amine,  CfiH5CH2NH2.  The  isocyanide  test  indicated  the  presence  of  a  primary 
amine.  The  reaction  with  benzene  sulfonyl  chloride  also  showed  this.  When  some 
of  the  free  amine  product  was  boiled  with  ammonium  hydroxide,  chlorine  was  found 
to  be  present  in  the  solution.  When  the  liquid  mixture  of  the  free  amines  stood  for 
a  few  days,  it  slowly  changed  to  a  hard,  brittle  solid. 

When  dry  hydrogen  chloride  was  passed  into  an  anhydrous  ether  solution  of  the 
amines  the  hydrochlorides  were  readily  formed  as  a  white  precipitate.  The  molecular 
weight  was  determined  by  solution  in  dil.  nitric  acid  and  precipitation  of  the  chloride 
as  silver  chloride.  Assuming  the  presence  of  only  one  amino  group  in  the  molecule 
this  gave  a  molecular  weight  of  273.5.  A  nitrogen  determination  of  the  hydrochloride 
by  the  absolute  method  gave  5.04%  of  nitrogen.  This  agrees  quite  closely  with  the 
theory  that  the  molecule  contains  but  one  amino  group.  The  hydrochloride  of  tetra- 
chloro-toluidine  contains  4.98%  of  nitrogen;  that  of  trichloro-toluidine  5.69%. 

Calc.  for  C7H,Cl4NH,HCl:  Cl,  63.1;  Calc.  for  C7H«C13NH2HC1:  Cl,  57.5.  Found: 
Cl,  59.0. 

The  only  important  features  of  the  work  with  benzyl  chloride  were  the  following. 
The  reaction  occurred  much  more  slowly.  No  amine  was  found  in  the  white  precipi- 
tate, unless  the  solution  had  been  exposed  to  sunlight,  or  allowed  to  stand  a  long  time. 
The  viscous  liquid  product  gradually  solidified  as  that  from  toluene  had  done. 

III.  Nitrogen  Trichloride  and  Benzene. — The  solutions  were  prepared  in  the 
usual  way.  This  reaction  took  place  much  more  slowly  than  did  the  reaction  with  tol- 
uene. The  main  chlorination  product  was  ben/ene  hexachloride.  The  white  pre- 
cipitate contained  no  amine,  unless  the  solution  was  allowed  to  stand  a  long  time  or 
had  been  exposed  to  sunlight.  The  benzene  solution  from  which  the  precipitate  had  been 
removed  was  shaken  with  enough  sodium  sulfite  solution  to  remove  any  free  chlorine. 
No  amine,  or  at  most  only  a  trace,  was  found  in  the  sulfite  solution.  The  benzene 
solution  did  not  now  have  the  yellow  color  of  free  chlorine,  nor  did  it  liberate  iodine 
from  potassium  iodide  readily,  as  a  solution  of  chlorine  would,  but  only  on  prolonged 
shaking.  This  nearly  colorless  benzene  solution  was  then  shaken  with  cone,  hydro- 
chloric acid.  The  benzene  turned  yellow  and  readily  liberated  iodine  from  potas- 
sium iodide,  and  the  aqueous  layer  was  found  to  contain  the  amines.  It  was  found 
that  the  benzene  solution  of  this  N-chloro-amine  could  be  concentrated  by  vacuum  dis- 
tillation. 

The  amount  of  the  amine  mixture  obtained  was  about  the  same  as  that  from  toluene. 
Most  of  the  tests  made  with  the  amines  from  toluene  were  carried  out  with  this  product. 
A  mixture  of  chloro-anilines  was  indicated,  The  viscous  liquid  mixture  of  the  free 
amines  did  not  solidify  on  standing;  but  on  treatment  with  ether  and  ligroin  gave  a 
crystalline  product.  The  hydrochloride  was  made  by  passing  dry  hydrogen  chloride  into 
an  anhydrous  ether  solution.  A  molecular  weight  determination  with  this  material 
gave  287.  The  molecular  weight  of  the  hydrochloride  of  tetrachloro-aniline  is  267.5, 
and  of  pentachloro-anilioe,  303. 

Summary. 

1.  Nitrogen  trichloride  reacts  with  ethyl  chloride  to  give,  among  other 
products,  ethylene  chloride.     This  compound  is  not  a  normal  product  of 


11 

the  action  of  free  chlorine  on  ethyl  chloride  in  the  absence  of  a  catalytic 
agent. 

2.  Nitrogen  trichloride  with  toluene  forms  benzyl  chloride    and    the 
monochloro-toluenes  together  with  higher  chlorinated  derivatives. 

3.  With  benzene  the  main  chlorination  product  is  benzene  hexachloride. 

4.  With  toluene,  with  benzene,  and  with  benzyl  chloride,  nitrogen  tri- 
chloride forms  small  amounts  of  N-chloro-amines. 

5.  The  N-chloro-amjne  group  of  the  compounds  formed  from  toluene 
and  benzyl  chloride  is  located  in  the  nucleus  and  not  in  the  side  chain. 

6.  The  chloro-amines  at  first  formed  are  acted  upon  further  by  the 
nitrogen  trichloride,  or  by  chlorine,  to  give  chlorinated  chloro-amines. 
From  benzene,  the  ultimate  product  is  probably  C-pentachloro-N-dichloro- 
aniline  C6C15NC12  but  such  a  compound  was  not  isolated. 

7.  The  chlorinations  referred  to  take  place  at  ordinary  temperatures, 
and  consequently  are  different  from  the  rearrangements  of  chloro-amines 
studied  by  Chattaway  and  Orton.11     In  this  regard  and  also  because  all 
of  the  hydrogen  atoms  of  the  benzene  nucleus  may  be  replaced  by  chlorine, 
they  resemble  the  chlorination  of  aniline  hydrochloride  by  chlorine.14 

8.  The  C-chloio-N-chloro-aniline  liberates  chlorine  on  treatment  with 
cone,  hydrochloric  acid  and  is  converted  to  C-chloro-aniline. 

9.  The  facts  established  are  most  easily  explained  by  assuming  that  the 
reactions  are  represented  by  the  following  equations. 


C6H6  +  NCl3  =  Cl(C8H6)NCl2  =  CttH5Na2  +  HC1 
NC13    +    4HC1  =  3C12    +    NH4C1. 

10.  The  free  chlorine  from  the  last  reaction  would  then  chlorinate 
the  chloro-amine. 

11.  The  formation  of  hydrochloric  acid  under  9  involves  a  change  of 
positive  chlorine  to  negative,  and  the  formation  of  considerable  quanti- 
ties of  free  nitrogen  may  be  connected  with  this  change. 


VITA. 

EDUCATIONAL  CAREER. 

B.  S.  Greenville  College,  1915. 

M.  S.  University  of  Illinois,  1919. 

Instructor  in  Chemistry  and  Physics. 

Chesbrough  Seminary,  North  Chili,  N.  Y.,  1915-17. 

Graduate  Assistant  in  Chemistry,  Univ.  of  111.,  1917-18. 

Research  Assistant  in  Chemistry,  Univ.  of  111.,  1918-21. 

PUBLICATIONS. 

Work  on  the  Conduct  of  Mixtures  of  Nitrogen  and  Chlorine  in  the 

Flaming  Arc.  IT.  A.  No  yes 

J.  Am.  Chem.  Soc  ,  43,  1774  (1921). 


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